Insulating fluid for thermal insulation

ABSTRACT

An insulating fluid system includes an acidic nanosilica dispersion and an alkaline activator. The acidic nanosilica dispersion includes silica nanoparticles and a stabilizer, such as a carboxylic acid. The alkaline activator includes an alkanolamine, such as a monoalkanolamine. A mixture of the acidic nanosilica dispersion and the alkaline activator forms an insulating fluid having a pH greater than 7 and less than or equal to 12, and the insulating fluid forms an insulating gel when heated to a temperature in a range between 100° F. and 300° F. The insulating gel may be formed in an annulus between an inner conduit and an outer conduit. The inner and outer conduits may be positioned in a subterranean formation. Forming an insulating gel may include combining the acidic nanosilica dispersion with the alkaline activator to yield the insulating fluid, and heating the insulating fluid to form the insulating gel.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a continuation of and claims the benefit of priorityto U.S. patent application Ser. No. 15/812,261, filed Nov. 14, 2017, thecontents of which are incorporated by reference herein.

TECHNICAL FIELD

This disclosure relates to an aqueous insulating fluid with low thermalconductivity for pipeline and subterranean applications.

BACKGROUND

Insulating fluids are often used in subterranean operations to insulatea hydrocarbon-containing fluid from the surrounding environment. Forinstance, if the surrounding environment is cold, insulating fluid canbe provided to an annulus between a first tubing through which ahydrocarbon-containing fluid flows and a second tubing or the walls of awell bore to reduce precipitation of heavier hydrocarbons, therebypromoting flow of the hydrocarbon-containing fluid through the firsttubing. Insulating fluids are also used for other insulatingapplications in which control of heat transfer is needed. Typicalinsulating fluids are formed by combining an alkaline nanosilicadispersion with an acidic activator such as phytic acid,methyglycinediacetic acid, or polyepoxysuccinic acid and are acidic,thereby contributing to corrosion downhole.

SUMMARY

In a first general aspect, an insulating fluid system includes an acidicnanosilica dispersion and an alkaline activator. The acidic nanosilicadispersion includes silica nanoparticles and a stabilizer. The alkalineactivator includes an alkanolamine. A mixture of the acidic nanosilicadispersion and the alkaline activator forms an insulating fluid having apH greater than 7 and less than or equal to 12, and the insulating fluidforms an insulating gel when heated to a temperature in a range between100 degrees Fahrenheit (° F.) and 300° F.

In a second general aspect, forming an insulating gel in an annulusbetween an inner conduit and an outer conduit includes combining analkaline activator with an acidic nanosilica dispersion to yield aninsulating fluid having a pH greater than 7 and less than or equal to12, providing the insulating fluid to the annulus, and heating theinsulating fluid in the annulus to a temperature in a range between 100°F. and 300° F., thereby forming an insulating gel in the annulus. Thealkaline activator includes an alkanolamine, and the acidic nanosilicadispersion includes silica nanoparticles and a stabilizer.

In a third general aspect, forming an insulating gel in an annulusbetween an inner conduit and an outer conduit includes providing anacidic nanosilica dispersion to the annulus, combining an alkalineactivator with the nanosilica dispersion in the annulus to yield aninsulating fluid having a pH greater than 7 and less than or equal to12, and heating the insulating fluid in the annulus to a temperature ina range between 100° F. and 300° F., thereby forming an insulating gelin the annulus. The acidic nanosilica dispersion includes silicananoparticles and a stabilizer, and the alkaline activator includes analkanolamine.

In a fourth general aspect, forming an insulating gel includes combiningan acidic nanosilica dispersion with an alkaline activator to yield aninsulating fluid having a pH greater than 7 and less than or equal to12, and heating the insulating fluid to a temperature in a range between100° F. and 300° F., thereby forming an insulating gel. The alkalineactivator includes an alkanolamine, the acidic nanosilica dispersionincludes silica nanoparticles and a stabilizer, and the stabilizer andthe alkanolamine react to yield a carboxamide.

Implementations of the first, second, third, and fourth general aspectsmay independently include one or more of the following features.

In some embodiments, the stabilizer includes a carboxylic acid. In someexamples, the carboxylic acid includes at least one of acetic acid,lactic acid, and citric acid. In some embodiments, the alkanolamineincludes at least one of monoethanolamine, diethanolamine, andtriethanolamine.

A pH of the acidic nanosilica dispersion is typically in a range between2 and 4. A particle size of the silica nanoparticles is typically in arange between 5 nanometers (nm) and 100 nm. The nanosilica dispersionmay include 5 weight percent (wt%) to 50 wt % of the silicananoparticles. A viscosity of the nanosilica dispersion at roomtemperature is in a range between 5 centipoise (cP) and 200 cP.

The insulating fluid may include 0.1 volume percent (vol %) to 20 vol %or 0.5 vol % to 20 vol % of the alkaline activator. The insulating fluidtypically forms an insulating gel in 2 hours (h) to 24 h when heated toa temperature in a range between 100° F. and 300° F.

Implementations of the second and third general aspects mayindependently include one or more of the following features.

In some embodiments, the inner conduit and the outer conduit arepositioned in a subterranean formation. The outer conduit may be awellbore. The second general aspect may further include flowing a fluidthrough the inner conduit. In one example, the fluid is ahydrocarbon-containing fluid.

Advantages of the compositions and methods described in this disclosureinclude ease of pumping due at least in part to the low viscosity of thepacker fluid composition, elimination of corrosion due at least in partto the alkaline nature of the final gelled packer fluid, controllablegel times, availability and cost effectiveness of materials, and ease ofoperational implementation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a system for forming an insulating gel in an annulusbetween an inner conduit and an outer conduit.

FIG. 2 is a flow chart for a first process for forming an insulatinggel.

FIG. 3 is a flow chart for a second process for forming an insulatinggel.

FIG. 4 is a flow chart for a third process for forming an insulatinggel.

FIG. 5 is a graph showing thermal insulating properties of an insulatinggel compared to thermal insulating properties of water.

DETAILED DESCRIPTION

Insulating fluids described in this disclosure utilize networkstructures formed from an aqueous acidic nanosilica dispersion and analkaline activator to yield an insulating gel having a low thermalconductivity. Forming a gel from the insulating fluid (“gelling”) can becontrolled by varying pH of the insulating fluid. A gel is considered tobe present when the viscosified insulating fluid cannot be sheared.Varying the pH of the insulating fluid can be achieved by varying theconcentration of the activator. In one example, gelling of theinsulating fluid is accelerated by increasing the pH of the insulatingfluid, with a greater pH typically resulting in faster gel formation.The delayed and controlled gelling of the insulating fluid allows theinsulating fluid to be prepared and pumped prior to gelling. Theinsulating gel does not degrade at temperatures up to 300° F., and isenvironmentally friendly.

The acidic nanosilica dispersion is an aqueous dispersion that includessilica nanoparticles and an acid. A size of the silica nanoparticles istypically in a range between 5 nm and 100 nm. As described, “size”generally refers to a diameter or largest dimension of the silicananoparticles. In one example, a size of the silica nanoparticles is ina range between 40 nm and 60 nm. The silica nanoparticles typicallycomprise 5 wt % to 50 wt % of the nanosilica dispersion. A viscosity ofthe nanosilica dispersion is typically in a range between 5 cP and 200cP at room temperature.

Suitable acids include organic acids (such as a carboxylic acid) andmineral acids (such as hydrochloric acid). The acid typically includesat least one of acetic acid, lactic acid, and citric acid. A pH of thenanosilica dispersion is typically in a range between 2 and 4. Asuitable nanosilica dispersion is IDISIL LPH35, available from EvonikCorporation. In some embodiments, the acidic nanosilica dispersionincludes one or more additives, such as glycerin, calcium carbonate,mica graphite, and the like, selected to increase rigidity of theresulting gel. In some embodiments, acidic nanosilica dispersionincludes 1 percent by volume (vol %) to 25 vol % of one or moreadditives.

The alkaline activator includes an alkanolamine. Combining the alkalineactivator and the acidic nanosilica dispersion does not result inprecipitation of silica nanoparticles ambient or elevated temperatures,for example in range of 100° F. to 300° F. Suitable alkanolaminesinclude monoethanolamine, diethanolamine, and triethanolamine.

The acidic nanosilica dispersion and the alkaline activator are combinedto yield an insulating fluid. The acidic nanosilica dispersion mayconsist of, or consist essentially of, the acidic nanosilica dispersionand the alkaline activator. In some embodiments, the acidic nanosilicadispersion and the alkaline activator are combined in a volume ratio ina range of 99:1 to 80:20 or 95:1 to 80:20. In one example, a molar ratioof nanosilica to monoethanolamine is 24:1. The insulating fluid has a pHgreater than 7. In some embodiments, the insulating fluid has a pH equalto or less than 12. In one example, the acidic nanosilica dispersionincludes acetic acid and the alkaline activator includesmonoethanolamine in such a ratio that the acetic acid and themonoethanolamine react to yield 2-(hydroxyl)ethylammonium acetate andN-(2-hydroxyethyl)acetamide, and the resulting insulating fluid has a pHgreater than 7.

The insulating fluid is heated to yield an insulating gel. In oneexample, heating the insulating fluid to a temperature in a rangebetween 100° F. and 300° F. yields an insulating gel in 2 h to 24 h. Therate of gelling of the insulating fluid can be controlled by selectingthe pH of the insulating fluid. Selecting the pH of the insulating fluidcan be achieved by adjusting the molar ratio of the acid in thenanosilica dispersion and the base in the alkaline activator. In oneexample, increasing the molar ratio of the base to the acid increasesthe pH of the insulating fluid (more alkaline) and accelerates formationof the insulating gel at a given temperature. In another example,decreasing the molar ratio of the base to the acid decreases the pH ofthe insulating fluid (less alkaline) and decelerates formation of theinsulating gel at a given temperature. In the pH range of 7 to 12, agreater pH typically results in faster gel formation. The ability todelay or control the length of time for gel formation allows theinsulating fluid to be premixed and pumped to a desired location, suchas a pipeline or subterranean formation.

In some embodiments, an insulating gel is formed in an annulus betweenan inner conduit and an outer conduit to reduce heat transfer into orout of the inner conduit. The inner conduit may be a tubing, such as aproduction tubing. The outer conduit may be a tubing or an opening, suchas a wellbore. Forming the insulating gel in the annulus thermallyinsulates the fluid from the surroundings outside the outer conduit. Insome embodiments, the inner conduit is a production tubing, and thefluid flowing through the inner conduit is a hydrocarbon-containingfluid. The insulating gel may be used to insulate thehydrocarbon-containing fluid, thereby promoting optimum recovery of thehydrocarbon-containing fluid. For instance, if the surroundingenvironment is cold, the insulating gel may inhibit transfer of heatfrom the hydrocarbon-containing fluid to the environment, maintaining atemperature of the hydrocarbon-containing fluid sufficient to avoidsolidification of heavier hydrocarbons and the accompanying reduction inflow rate. In some cases, the insulating gel may prevent collapse of acasing in a wellbore. Insulating gels formed as described in thisdisclosure may also be used in other applications and with other fluidsfor which the control of heat transfer is desirable. Insulating gelsdescribed in this disclosure do not degrade at temperatures up to 300°F., remaining in gel form to inhibit convection currents fromtransferring heat from the fluid in the inner conduit to theenvironment.

FIG. 1 depicts system 100 for providing an insulating fluid orcomponents of an insulating fluid system to an annulus 102 between firstconduit 104 and second conduit 106 in a subterranean formation. In someembodiments, the insulating fluid can be prepared and provided toannulus 102 as a single pill. In other embodiments, the acidicnanosilica dispersion is provided to annulus 102 first, and the alkalineactivator is provided later.

FIG. 2 is a flow chart showing operations in process 200 for forming aninsulating gel in an annulus between an inner conduit and an outerconduit. In some embodiments, the inner conduit and the outer conduitare in a wellbore. In other embodiments, the inner conduit and outerconduit form part of a pipeline or other fluid flow system. In 202, analkaline activator is combined with an acidic nanosilica dispersion toyield an insulating fluid. The insulating fluid typically has a pHgreater than 7 and less than or equal to 12. In 204, the insulatingfluid is provided to the annulus. In 206, the insulating fluid in theannulus is heated, thereby forming an insulating gel. The insulatingfluid is typically heated to a temperature in a range between 100° F.and 300° F. The insulating gel typically forms in 2 h to 24 h. The innerconduit may be a production tubing, and a hydrocarbon-containing fluidmay be flowing through the production tubing.

FIG. 3 is a flow chart showing operations in process 300 for forming aninsulating gel in an annulus between an inner conduit and an outerconduit. In some embodiments, the inner conduit and the outer conduitare in a wellbore. In other embodiments, the inner conduit and outerconduit form part of a pipeline or other fluid flow system. In 302, anacidic nanosilica dispersion is provided to the annulus. In 304, analkaline activator is combined with the nanosilica dispersion in theannulus to yield an insulating fluid. The insulating fluid typically hasa pH greater than 7 and less than or equal to 12. In 306, the insulatingfluid is heated in the annulus to form an insulating gel in the annulus.The insulating fluid is typically heated to a temperature in a rangebetween 100° F. and 300° F. The insulating gel typically forms in 2hours to 24 hours. The inner conduit may be a production tubing, and ahydrocarbon-containing fluid may be flowing through the productiontubing.

FIG. 4 is a flow chart showing operations in process 400 for forming aninsulating gel. In some embodiments, the insulating gel is formed in asubterranean formation. In 402, an acidic nanosilica dispersion iscombined with an alkaline activator to yield an insulating fluid. Theinsulating fluid typically has a pH greater than 7 and less than orequal to 12. In 404, the insulating fluid is heated to form aninsulating gel. The insulating fluid is typically heated to atemperature in a range between 100° F. and 300° F. The insulting geltypically forms in 2 h to 24 h.

EXAMPLE

2 milliliters (mL) monoethanolamine (available from SABIC) was addedover 5 minutes to 120 mL of an acidic nanosilica dispersion (IDISILLPH35, from Evonik Corporation) with constant stirring to yield aninsulating fluid. Properties of IDISIL LPH35 are listed in Table 1. Theinitial pH of acidic nanosilica dispersion was measured to be 3.6. ThepH of the nanosilica dispersion after addition monoethanolamine was9.28. This nanosilica dispersion was then placed in a high temperature,high pressure (HTHP) aging cell at 500 pounds per square inch (psi). Thecell was placed in an oven and heated at 300° F. for 16 hours. After 16hours of static aging at 300° F., the insulating fluid had formed agelled solid, suitable for use as an insulating packer fluid. In Table1, “g” represents “grams” and “° C.” represents “degrees Celsius.”

TABLE 1 Typical properties of IDISIL LPH35 pH at Specific Viscosity atVisual 25° C. Gravity (g/mL) 25° C. (cP) Stabilizer Appearance 2-4 1.230 acetic acid white/off white

Thermal insulation properties of the insulating gel were compared withthermal insulation properties of water. A graduated cylinder was placedin each of two 400 mL glass beakers. Water (75° F.) was added to one ofthe glass beakers and the prepared insulating gel (75° F.) was added tothe other glass beaker to surround the graduated cylinders. 20 mL waterheated to 110° F. was poured into each graduated cylinder. A temperatureindicator was positioned in each of the graduated cylinders, and theinsulating properties were compared by recording the time taken for thehot water placed in the measuring cylinders to reach 80.9° F. Plots 500and 502 in FIG. 5 show temperature of the water in the graduatedcylinder as function of time in minutes for beakers with insulating geland water, respectively. As shown in FIG. 5, the time for the hot watersurrounded by the insulating gel to cool from 110° F. to 80.9° F. was 32minutes (min), while the time for the hot water surrounded by water tocool from 110° F. to 80.9° F. was 8 min. The time difference of 24 minshows that the heat loss in the case of the insulating packer fluid ismuch less than in the case of water.

Other aspects, advantages, and modifications of this disclosure arewithin the scope of the following claims.

What is claimed is:
 1. An insulating fluid system for a wellbore in asubterranean formation, comprising: an acidic nanosilica dispersion tocombine with an alkaline activator to give an insulating fluid toinsulate production tubing in the wellbore, wherein the acidicnanosilica dispersion comprises silica nanoparticles and a stabilizer,wherein pH of the acidic nanosilica dispersion is in a range of 2 to 4,and wherein viscosity of the acidic nanosilica dispersion at roomtemperature is in a range of 5 centipoise (cP) to 200 cP; and thealkaline activator to combine with the acidic nanosilica dispersion togive the insulating fluid having a pH in a range of 7 to 12 to activatethe acidic nanosilica dispersion, wherein the alkaline activatorcomprises an alkanolamine, and wherein the insulating fluid forms aninsulating gel in 2 to 24 hours at a temperature in a range of 100° F.and 300° F.
 2. The insulating fluid system of claim 1, wherein thestabilizer comprises carboxylic acid comprising at least one of aceticacid, lactic acid, or citric acid, wherein the alkanolamine comprises atleast one of monoethanolamine, diethanolamine, or triethanolamine, andwherein a volume ratio of the acidic nanosilica dispersion to thealkaline activator is at least 80:20.
 3. The insulating fluid system ofclaim 1, wherein the stabilizer comprises acetic acid, wherein thealkanolamine comprises monoethanolamine at a ratio to the acetic acidsuch that combining of the alkaline activator with the acidic nanosilicadispersion yields 2-(hydroxyl)ethylammonium acetate andN-(2-hydroxyethyl)acetamide.
 4. The insulating fluid system of claim 1,wherein the silica nanoparticles comprise a particle size is in a rangeof 5 nanometers (nm) to 100 nm, and wherein the silica nanoparticles arein a range of 5 weight percent (wt %) to 50 wt % of the acidicnanosilica dispersion.
 5. The insulating fluid system of claim 1,wherein the acidic nanosilica dispersion comprises at least one ofglycerin, calcium carbonate, or mica graphite, and wherein combining thealkaline activator and the acidic nanosilica dispersion does not resultin precipitation of the silica nanoparticles.
 6. An insulating fluid fora wellbore in a subterranean formation, the insulating fluid comprising:a mixture of an acidic nanosilica dispersion having a pH in a range of 2to 4 with an alkaline activator, the insulating fluid having a pH in arange of 7 to 12 to insulate production tubing in the wellbore, whereinthe acidic nanosilica dispersion comprises silica nanoparticles and anacid, wherein the alkaline activator comprises an alkanolamine toactivate the acidic nanosilica dispersion, and wherein the insulatingfluid forms an insulating gel in 2 to 24 hours at a temperature in arange of 100° F. and 300° F.
 7. The insulating fluid of claim 6, whereinthe alkaline activator comprises less than 20 volume percent of theinsulating fluid, and wherein the insulating fluid does not compriseprecipitation of the silica nanoparticles.
 8. The insulating fluid ofclaim 6, wherein the acidic nanosilica dispersion comprises at least oneof glycerin, calcium carbonate, or mica graphite, and wherein theinsulating fluid is disposed adjacent the wellbore for pumping into thewellbore.
 9. The insulating fluid of claim 6, wherein the acid comprisescarboxylic acid comprising at least one of acetic acid, lactic acid, orcitric acid, wherein the alkanolamine comprises at least one ofmonoethanolamine, diethanolamine, or triethanolamine, and wherein timeto gel formation of the insulating fluid at the temperature in the rangeof 100° F. and 300° F. is inversely proportional with the pH of theinsulating fluid in the range of 7 to
 12. 10. The insulating fluid ofclaim 6, wherein the silica nanoparticles comprise a particle size in arange of 5 nanometers (nm) to 100 nm, wherein the silica nanoparticlesare in a range of 5 weight percent (wt %) to 50 wt % of the acidicnanosilica dispersion, and wherein greater pH of the insulating fluid inthe range of 7 to 12 accelerates formation of the insulating gelcompared to lower pH of the insulating fluid in the range of 7 to 12.11. An insulating gel comprising a gel of an acidic nanosilicadispersion and an alkaline activator, the insulating gel disposed in awellbore in a subterranean formation and having a pH in a range of 7 to12 and a temperature in a range of 100° F. and 300° F., wherein theacidic nanosilica dispersion comprises silica nanoparticles and astabilizer, and wherein the alkaline activator comprises an alkanolaminethat activates the acidic nanosilica dispersion for gel formation. 12.The insulating gel of claim 11, wherein the insulating gel is disposedin an annulus between a production tubing and a wall of the wellbore.13. The insulating gel of claim 11, wherein the stabilizer comprisescarboxylic acid comprising at least one of acetic acid, lactic acid, orcitric acid, wherein the alkanolamine comprises at least one ofmonoethanolamine, diethanolamine, or triethanolamine, wherein the gelformation of the insulating gel occurs over a time period in a range of2 hours to 24 hours at the temperature in the range of 100° F. and 300°F., and wherein length of the time period is correlative inversely withthe pH.
 14. The insulating gel of claim 11, wherein the silicananoparticles comprise a particle size is in a range of 5 nanometers(nm) to 100 nm, wherein the silica nanoparticles are in a range of 5weight percent (wt %) to 50 wt % of the acidic nanosilica dispersionwherein the insulating gel does not comprise precipitation of the silicananoparticles.
 15. The insulating gel of claim 11, wherein thestabilizer comprises acetic acid, wherein the acidic nanosilicadispersion comprises a pH in a range of 2 to 4, wherein the alkanolaminecomprises monoethanolamine, and wherein the insulating gel comprises2-(hydroxyl) ethylammonium acetate and N-(2-hydroxyethyl)acetamide inthe insulating gel.
 16. A wellbore in a subterranean formation, thewellbore comprising: production tubing; and an insulating gel thatinsulates the production tubing, the insulating gel comprising a gelformed from a mixture of an acidic nanosilica dispersion and an alkalineactivator, the insulating gel having a pH in a range of 7 to 12 and atemperature in a range of 100° F. and 300° F., wherein the acidicnanosilica dispersion comprises silica nanoparticles and a stabilizer,and wherein the alkaline activator comprises an alkanolamine thatactivates the acidic nanosilica dispersion for gel formation.
 17. Thewellbore of claim 16, wherein the insulating gel is disposed in anannulus between the production tubing and a wall of the wellbore,wherein the gel formation of the insulating gel occurs over a timeperiod in a range of 2 hours to 24 hours at the temperature in the rangeof 100° F. and 300° F., and wherein length of the time period iscorrelative inversely with the pH.
 18. The wellbore of claim 16, whereinthe stabilizer comprises carboxylic acid comprising at least one ofacetic acid, lactic acid, or citric acid, and wherein the alkanolaminecomprises at least one of monoethanolamine, diethanolamine, ortriethanolamine.
 19. The wellbore of claim 16, wherein the silicananoparticles comprise a particle size is in a range of 5 nanometers(nm) to 100 nm, wherein the silica nanoparticles are in a range of 5weight percent (wt %) to 50 wt % of the acidic nanosilica dispersion.20. The wellbore of claim 16, wherein the stabilizer comprises aceticacid, wherein the alkanolamine comprises monoethanolamine, and whereinthe insulating gel comprises 2-(hydroxyl)ethylammonium acetate andN-(2-hydroxyethyl)acetamide.